CN115505292A - UV frosted ink and preparation method thereof - Google Patents
UV frosted ink and preparation method thereof Download PDFInfo
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- CN115505292A CN115505292A CN202211325082.8A CN202211325082A CN115505292A CN 115505292 A CN115505292 A CN 115505292A CN 202211325082 A CN202211325082 A CN 202211325082A CN 115505292 A CN115505292 A CN 115505292A
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 claims abstract description 33
- 239000004814 polyurethane Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000013543 active substance Substances 0.000 claims abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 18
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000012190 activator Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 10
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 8
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 4
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 claims description 2
- VVNRQZDDMYBBJY-UHFFFAOYSA-M sodium 1-[(1-sulfonaphthalen-2-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 VVNRQZDDMYBBJY-UHFFFAOYSA-M 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000976 ink Substances 0.000 description 59
- -1 polydimethylsiloxane Polymers 0.000 description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 7
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- BBAGPRAUWBSYDH-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O BBAGPRAUWBSYDH-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses UV frosted ink which comprises the following raw materials in parts by weight: 10-20 parts of polyurethane prepolymer, 5-15 parts of UV gloss oil, 0.1-1 part of dibutyltin dilaurate, 2-6 parts of polyethylene glycol acrylate, 3-8 parts of acrylic functional monomer, 40-55 parts of activator, 2-5 parts of photoinitiator, 10-15 parts of additive and 1-10 parts of pigment. The acrylic acid functional monomer is obtained by reacting 4-semicarbazide pyrimidine with isocyano ethyl methacrylate. The invention discloses a preparation method of the UV frosted ink, which comprises the steps of dropwise adding dibutyltin dilaurate into a polyurethane prepolymer, dropwise adding polyethylene glycol acrylate, stirring, defoaming in vacuum, adding an acrylic acid functional monomer, uniformly stirring, adding deionized water, and stirring to obtain a water-based composite polyurethane emulsion; and adding UV gloss oil, an active agent, a photoinitiator, a pigment and an additive into the water-based composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Description
Technical Field
The invention relates to the technical field of frosted ink, in particular to UV frosted ink and a preparation method thereof.
Background
In recent years, with the rapid development of industry, the problems of environmental pollution and ecological deterioration are becoming more and more noticeable, and the importance of protecting the ecological environment has been recognized. The development of science and technology not only needs to promote the sustainable development of economy and society, but also ensures the sustainable development of ecology for human life, and the green science and technology becomes the mainstream of scientific development. In response to this trend, ultraviolet (UV) curing systems have been developed and are now an extremely active area of research and development.
Aqueous UV curable inks combine the advantages of both UV curable inks and aqueous inks. The UV curing ink uses water to replace a reactive diluent, so that the problems of pollution, irritation and the like caused by using Volatile Organic Compounds (VOCs) in the UV curing ink are solved, and a novel curing means is provided for the water-based ink.
The curing mechanism of the water-based UV printing ink is that ultraviolet rays with certain wavelength are used for irradiating the water-based UV printing ink to excite an photoinitiator to generate active free radicals, and the prepolymer and the monomer are initiated to generate a crosslinking reaction instantly, so that a liquid state is converted into a solid state.
The existing water-based UV frosted ink has the technical problems of poor stability, poor wear resistance, easy brittle collapse and detachment of a film layer due to stress and poor adhesive force of the film layer, which are required to be solved at present.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides UV frosted ink and a preparation method thereof.
The UV frosted ink comprises the following raw materials in parts by weight: 10-20 parts of polyurethane prepolymer, 5-15 parts of UV gloss oil, 0.1-1 part of dibutyltin dilaurate, 2-6 parts of polyethylene glycol acrylate, 3-8 parts of acrylic functional monomer, 40-55 parts of activator, 2-5 parts of photoinitiator, 10-15 parts of additive and 1-10 parts of pigment.
Preferably, the acrylic functional monomer is obtained by reacting an amino group with an isocyano group using 4-semicarbazide pyrimidine and isocyanoethyl methacrylate.
Preferably, the mass ratio of the 4-semicarbazide pyrimidine to the isocyano ethyl methacrylate is 1-2:2-6.
Preferably, the acrylic acid functional monomer is prepared by the following specific steps: adding 4-semicarbazide pyrimidine into dimethyl sulfoxide, heating to 140-160 ℃ under a stirring state, then adding isocyano ethyl methacrylate, continuously stirring for 1-5min, cooling to room temperature, adding methanol for precipitation, filtering, and drying in vacuum to obtain the acrylic acid functional monomer.
Preferably, the active agent consists of a reactive diluent and a surfactant in a mass ratio of 10:1-2, and mixing.
Preferably, the pigment is at least one of phthalocyanine blue, lithol red, lemon yellow, titanium dioxide and carbon black.
Preferably, the photoinitiator is at least one of 2,4, 6-trimethylbenzoylphosphonic acid ethyl ester, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone, 2-isopropyl thioxanthone and methyl o-benzoylbenzoate.
Preferably, the additive is at least one of a leveling agent, a film forming assistant, a water-based defoaming agent, an ultraviolet absorber and a wetting dispersant.
The preparation method of the UV frosted ink comprises the following steps:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer under the stirring state, adjusting the temperature to 50-70 ℃, dropwise adding polyethylene glycol acrylate, stirring for 10-15h, defoaming in vacuum, adding acrylic acid functional monomers, stirring uniformly, adding deionized water, and stirring at the speed of 500-1500r/min for 1-2h to obtain a water-based composite polyurethane emulsion;
(2) And adding UV gloss oil, an active agent, a photoinitiator, a pigment and an additive into the water-based composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
The using method of the UV frosted ink comprises the steps of printing the UV frosted ink, and then placing the printed UV frosted ink in a UV oven with the wavelength of 365nm for illumination polymerization for 1-2h.
The technical effects of the invention are as follows:
the invention adopts the polyethylene glycol acrylate to seal the end of the polyurethane, and then the polyurethane is copolymerized with the acrylic acid functional monomer, the polyurethane sealed by the polyethylene glycol acrylate has good hydrophilicity and is combined with the acrylic acid functional monomer, the functional side chain on the polyurethane is self-assembled to form a three-dimensional cross-linking structure based on multiple hydrogen bonds and can undergo continuous dissociation and reconstruction, so that the product has self-healing property after being damaged, and meanwhile, the functional side chain can play a role of a cross-linking point in the polyurethane macromolecular structure sealed by the polyethylene glycol acrylate, thereby leading the whole system to have excellent stability.
The aqueous composite polyurethane emulsion obtained by the invention forms a basic skeleton of the UV ink, the performance of the aqueous composite polyurethane emulsion plays a key role in the performance of an ink film after the ink is cured, when the surface of the obtained UV frosted ink bears higher stress, hydrogen bonds are broken to absorb energy, and when the external force is cancelled, the hydrogen bonds are reformed, so that the excellent wear resistance of the surface of the film layer is realized, the system is highly crosslinked and combined, the stress is effectively transmitted and dispersed, the film layer is further prevented from being broken and separated in the stress process, and the comprehensive effect ensures that the wear resistance of the film layer can be obviously improved.
Meanwhile, the product has better adhesion fastness to the PET film, and because the acrylic acid functional monomer in the obtained water-based composite polyurethane emulsion can form hydrogen bonds with polar groups on the surface of the PET film, the adhesion strength is effectively enhanced.
The invention has strong adhesive force, can be well adhered to a printing stock, has high stability and good wear resistance, does not have the problems of cracking and air holes after the solidification is finished, does not contain organic solvent, is green and environment-friendly, and is convenient for large-scale popularization and application.
Drawings
FIG. 1 is a Taber abrasion index comparison chart of UV frosted inks obtained in example 5 and comparative examples 1-2.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
The UV frosted ink comprises the following raw materials: 10kg of polyurethane prepolymer, 5kg of UV gloss oil, 0.1kg of dibutyltin dilaurate, 2kg of polyethylene glycol acrylate, 3kg of acrylic functional monomer, 40kg of activating agent, 2kg of ethyl 2,4, 6-trimethylbenzoyl phosphonate, 10kg of polydimethylsiloxane and 1kg of pigment.
The acrylic acid functional monomer is prepared by the following specific steps: adding 1kg of 4-semicarbazide pyrimidine into 10kg of dimethyl sulfoxide, heating to 140 ℃ under a stirring state, adding 2kg of isocyano ethyl methacrylate, continuing stirring for 1min, cooling to room temperature, adding methanol for precipitation, filtering, and drying in vacuum to obtain the acrylic functional monomer.
The active agent is prepared from an active diluent PEC (Shanghai polymeric micro-coating auxiliary agent Co., ltd.) and cocamidopropyl betaine according to the mass ratio of 10:1 by mixing.
The preparation method of the UV frosted ink comprises the following steps:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer under the stirring state, adjusting the temperature to 50 ℃, dropwise adding polyethylene glycol acrylate, stirring for 10h, defoaming in vacuum, adding an acrylic acid functional monomer, stirring uniformly, adding deionized water, and stirring for 1h at the speed of 500r/min to obtain a water-based composite polyurethane emulsion;
(2) And adding UV gloss oil, an active agent, 2,4, 6-trimethyl benzoyl ethyl phosphonate, a pigment and polydimethylsiloxane into the aqueous composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Example 2
The UV frosted ink comprises the following raw materials: 20kg of polyurethane prepolymer, 15kg of UV gloss oil, 1kg of dibutyltin dilaurate, 6kg of polyethylene glycol acrylate, 8kg of acrylic functional monomer, 55kg of active agent, 5kg of 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-acetone, 10kg of polydimethylsiloxane, 5kg of propylene glycol monomethyl ether acetate and 10kg of pigment.
The active agent is prepared from an active diluent PEC (Shanghai polymeric micro-coating auxiliary agent Co., ltd.) and cocamidopropyl betaine according to the mass ratio of 10:2, mixing the components.
The acrylic acid functional monomer is prepared by the following specific steps: adding 2kg of 4-semicarbazide pyrimidine into 20kg of dimethyl sulfoxide, heating to 160 ℃ under a stirring state, then adding 6kg of isocyano ethyl methacrylate, continuously stirring for 5min, cooling to room temperature, adding methanol for precipitation, filtering, and drying in vacuum to obtain the acrylic acid functional monomer.
The preparation method of the UV frosted ink comprises the following steps:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer under the stirring state, adjusting the temperature to 50-70 ℃, dropwise adding polyethylene glycol acrylate, stirring for 15h, defoaming in vacuum, adding an acrylic acid functional monomer, stirring uniformly, adding deionized water, and stirring at the speed of 1500r/min for 2h to obtain a water-based composite polyurethane emulsion;
(2) Adding UV gloss oil, an active agent, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-acetone, a pigment, polydimethylsiloxane and propylene glycol monomethyl ether acetate into the aqueous composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Example 3
The UV frosted ink comprises the following raw materials: 13kg of polyurethane prepolymer, 12kg of UV gloss oil, 0.3kg of dibutyltin dilaurate, 5kg of polyethylene glycol acrylate, 4kg of acrylic functional monomer, 50kg of active agent, 3kg of 2-isopropyl thioxanthone, 5kg of polydimethylsiloxane, 5kg of propylene glycol monomethyl ether acetate, 4kg of ultraviolet absorbent UV-P and 2kg of pigment.
The active agent is prepared from an active diluent PEC (Shanghai polymeric micro-coating auxiliary agent Co., ltd.) and cocamidopropyl betaine according to the mass ratio of 10:1.8 and mixing.
The acrylic acid functional monomer is prepared by the following specific steps: adding 1.7kg of 4-semicarbazide pyrimidine into 13kg of dimethyl sulfoxide, heating to 155 ℃ under stirring, adding 3kg of isocyano ethyl methacrylate, continuing stirring for 4min, cooling to room temperature, adding methanol for precipitation, filtering, and vacuum drying to obtain the acrylic acid functional monomer.
The preparation method of the UV frosted ink comprises the following steps:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer under the stirring state, adjusting the temperature to 55 ℃, dropwise adding polyethylene glycol acrylate, stirring for 14h, defoaming in vacuum, adding an acrylic acid functional monomer, stirring uniformly, adding deionized water, and stirring at the speed of 800r/min for 1.7h to obtain a water-based composite polyurethane emulsion;
(2) Adding UV gloss oil, an active agent, 2-isopropyl thioxanthone, a pigment, polydimethylsiloxane, propylene glycol monomethyl ether acetate and an ultraviolet absorbent UV-P into the aqueous composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Example 4
The UV frosted ink comprises the following raw materials: 17kg of polyurethane prepolymer, 8kg of UV gloss oil, 0.7kg of dibutyltin dilaurate, 3kg of polyethylene glycol acrylate, 6kg of acrylic acid functional monomer, 45kg of active agent, 4kg of methyl o-benzoylbenzoate, 4kg of polydimethylsiloxane, 12kg of alcohol ester, 4kg of ultraviolet absorbent UV-P and 6kg of pigment.
The active agent is prepared from a reactive diluent PEC (Shanghai polymeric micro-coating assistant Co., ltd.) and cocamidopropyl betaine according to the mass ratio of 10:1.2 and mixing.
The acrylic acid functional monomer is prepared by the following specific steps: adding 1.3kg of 4-semicarbazide pyrimidine into 17kg of dimethyl sulfoxide, heating to 145 ℃ under a stirring state, adding 5kg of isocyano ethyl methacrylate, continuing stirring for 2min, cooling to room temperature, adding methanol for precipitation, filtering, and drying in vacuum to obtain the acrylic functional monomer.
The preparation method of the UV frosted ink comprises the following steps:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer under the stirring state, adjusting the temperature to 65 ℃, dropwise adding polyethylene glycol acrylate, stirring for 12h, defoaming in vacuum, adding an acrylic acid functional monomer, stirring uniformly, adding deionized water, and stirring at the speed of 1200r/min for 1.3h to obtain a water-based composite polyurethane emulsion;
(2) Adding UV gloss oil, an active agent, methyl o-benzoylbenzoate, a pigment, polydimethylsiloxane, alcohol ester 12 and an ultraviolet absorbent UV-P into the water-based composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Example 5
The UV frosted ink comprises the following raw materials: 15kg of polyurethane prepolymer, 10kg of UV gloss oil, 0.5kg of dibutyltin dilaurate, 4kg of polyethylene glycol acrylate, 5kg of acrylic functional monomer, 48kg of active agent, 3.5kg of 1-hydroxy-cyclohexyl-phenyl ketone, 5kg of polydimethylsiloxane, 12 5kg of alcohol ester, UV-531 kg of ultraviolet absorbent and 4kg of pigment.
The active agent is prepared from an active diluent PEC (Shanghai polymeric micro-coating auxiliary agent Co., ltd.) and cocamidopropyl betaine according to the mass ratio of 10:1.5 mixing.
The acrylic acid functional monomer is prepared by the following specific steps: adding 1.5kg of 4-semicarbazide pyrimidine into 15kg of dimethyl sulfoxide, heating to 150 ℃ under the stirring state, then adding 4kg of isocyano ethyl methacrylate, continuing stirring for 3min, cooling to room temperature, adding methanol for precipitation, filtering, and drying in vacuum to obtain the acrylic acid functional monomer.
The preparation method of the UV frosted ink comprises the following steps:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer in a stirring state, adjusting the temperature to 60 ℃, dropwise adding polyethylene glycol acrylate, stirring for 13h, defoaming in vacuum, adding an acrylic acid functional monomer, stirring uniformly, adding deionized water, and stirring at the speed of 1000r/min for 1.5h to obtain a water-based composite polyurethane emulsion;
(2) Adding UV gloss oil, an active agent, 1-hydroxy-cyclohexyl-phenyl ketone, a pigment, polydimethylsiloxane, alcohol ester 12 and an ultraviolet absorbent UV-531 into the aqueous composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Comparative example 1
The UV frosted ink comprises the following raw materials: 15kg of polyurethane prepolymer, 10kg of UV gloss oil, 0.5kg of dibutyltin dilaurate, 4kg of polyethylene glycol acrylate, 5kg of isocyanatoethyl methacrylate, 48kg of active agent, 3.5kg of 1-hydroxy-cyclohexyl-phenyl ketone, 5kg of polydimethylsiloxane, 12 5kg of alcohol ester, 3kg of ultraviolet absorbent UV-531 kg and 4kg of pigment.
The active agent is prepared from an active diluent PEC (Shanghai polymeric micro-coating auxiliary agent Co., ltd.) and cocamidopropyl betaine according to the mass ratio of 10:1.5 mixing.
The preparation method of the UV frosted ink comprises the following steps:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer under the stirring state, adjusting the temperature to 60 ℃, dropwise adding polyethylene glycol acrylate, stirring for 13h, defoaming in vacuum, adding isocyano ethyl methacrylate, stirring uniformly, adding deionized water, and stirring at the speed of 1000r/min for 1.5h to obtain a water-based composite polyurethane emulsion;
(2) Adding UV gloss oil, an active agent, 1-hydroxy-cyclohexyl-phenyl ketone, a pigment, polydimethylsiloxane, alcohol ester 12 and an ultraviolet absorbent UV-531 into the water-based composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Comparative example 2
The UV frosted ink comprises the following raw materials: 24.5kg of aqueous polyurethane emulsion, 10kg of UV gloss oil, 48kg of an active agent, 3.5kg of 1-hydroxy-cyclohexyl-phenyl ketone, 5kg of polydimethylsiloxane, 12kg of alcohol ester, UV-531 kg of an ultraviolet absorbent and 4kg of pigment.
The active agent is prepared from an active diluent PEC (Shanghai polymeric micro-coating auxiliary agent Co., ltd.) and cocamidopropyl betaine according to the mass ratio of 10:1.5 mixing.
The preparation method of the UV frosted ink comprises the following steps: adding UV gloss oil, an active agent, 1-hydroxy-cyclohexyl-phenyl ketone, a pigment, polydimethylsiloxane, alcohol ester 12 and an ultraviolet absorbent UV-531 into the aqueous polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
Referring to the method for testing the adhesion fastness of GB/T13217.7-2009 liquid ink, the UV frosted ink obtained in example 5 and comparative examples 1-2 is coated on a PET film by using a silk rod and is placed for 24 hours. The adhesive tape is adhered on the printing ink surface, and is quickly peeled off after being uniformly kneaded, the state of the printing surface after being peeled off is observed, and more than 90% of the residual printing film is good; 60-90% of the printing film residue is qualified; the printed film remaining 60% or less was poor.
| Fastness to adhesion to PET film | |
| Example 5 | Good effect |
| Comparative example 1 | Is poor |
| Comparative example 2 | Is poor |
From the above table it can be seen that: the UV matte ink obtained in example 5 had the highest adhesion. The applicant believes that: the acrylic acid functional monomer in the aqueous composite polyurethane emulsion can form hydrogen bonds with polar groups on the surface of the PET film, so that the adhesion strength is effectively enhanced.
The UV frosted inks obtained in example 5 and comparative examples 1-2 were subjected to stability testing as follows: 100g of each group of samples are put into a test cup, the storage stability is simulated through an accelerated sedimentation test of a centrifugal machine, and after the centrifugal machine is set to carry out centrifugal sedimentation for 15min at the rotating speed of 3000r/min, if no sediment exists, the storage stability period of the test cup can reach 6 months.
| Stability of | |
| Example 5 | Without precipitation |
| Comparative example 1 | Less amount of precipitate |
| Comparative example 2 | Less amount of precipitate |
From the above table it can be seen that: the UV matte ink obtained in example 5 had the best stability. The applicant believes that: the invention adopts the polyethylene glycol acrylate to carry out end capping on the polyurethane, and then carries out copolymerization with the acrylic acid functional monomer, the polyurethane capped by the polyethylene glycol acrylate has good hydrophilicity, is combined with the acrylic acid functional monomer, and has a three-dimensional cross-linking structure based on multiple hydrogen bonds formed by self-assembly of functional side chains thereon, and can undergo continuous de-association and reconstruction, so that the product has self-healing property after being damaged, and simultaneously, the functional side chains can play a role of cross-linking points in the polyurethane macromolecular structure capped by the polyethylene glycol acrylate, thereby leading the whole system to have excellent stability.
The UV frosted inks obtained in example 5 and comparative examples 1-2 were subjected to abrasion resistance tests as follows: and coating each group of samples by using a No. 3 wire rod through a coating machine, and curing the samples through an ultraviolet curing machine. The abrasion resistance of the sample film layer is tested by using a Taber abrasion tester, and the abrasion resistance is characterized by a Taber abrasion index.
Taber abrasion index = (M) 0 -M r )×1000/r
In the formula, M 0 Is the mass of the sample before it is worn; m r Is the mass of the sample after wear; r is the experimental number of revolutions.
As shown in fig. 1, the UV frosted ink obtained in example 5 has the best abrasion resistance. The applicant believes that: the UV frosted ink adopts the water-based composite polyurethane emulsion as the basic framework of the UV ink, the performance of the UV frosted ink plays a key role in the performance of the ink film after the ink is solidified, when the surface of the obtained UV frosted ink bears higher stress, hydrogen bonds are broken to absorb energy, and when the external force is cancelled, the hydrogen bonds are reformed, so that the surface of the film layer has excellent wear resistance, the system is highly cross-linked and combined, the stress is effectively transmitted and dispersed, the film layer is further prevented from being broken off in the stress process, and the comprehensive effect ensures that the wear resistance of the film layer can be obviously improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The UV frosted ink is characterized by comprising the following raw materials in parts by weight: 10-20 parts of polyurethane prepolymer, 5-15 parts of UV gloss oil, 0.1-1 part of dibutyltin dilaurate, 2-6 parts of polyethylene glycol acrylate, 3-8 parts of acrylic functional monomer, 40-55 parts of activator, 2-5 parts of photoinitiator, 10-15 parts of additive and 1-10 parts of pigment;
the acrylic acid functional monomer is obtained by reacting 4-semicarbazide pyrimidine with isocyano ethyl methacrylate.
2. The UV frosted ink according to claim 2, wherein the mass ratio of 4-semicarbazide pyrimidine to isocyano ethyl methacrylate is 1-2:2-6.
3. The UV frosted ink according to claim 1 or 2, wherein the acrylic functional monomer is prepared by the following specific steps: adding 4-semicarbazide pyrimidine into dimethyl sulfoxide, heating to 140-160 ℃ under a stirring state, then adding isocyano ethyl methacrylate, continuously stirring for 1-5min, cooling to room temperature, adding methanol for precipitation, filtering, and drying in vacuum to obtain the acrylic acid functional monomer.
4. The UV frosting ink according to claim 1, wherein the active agent is prepared from a reactive diluent and a surfactant in a mass ratio of 10:1-2, and mixing.
5. The UV frosted ink according to claim 1, wherein the pigment is at least one of phthalocyanine blue, lithol red, lemon yellow, titanium dioxide and carbon black.
6. The UV frosting ink according to claim 1, wherein the photoinitiator is at least one of ethyl 2,4, 6-trimethylbenzoylphosphonate, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone, 2-isopropyl thioxanthone, and methyl o-benzoylbenzoate.
7. The UV frosted ink according to claim 1, wherein the additive is at least one of a leveling agent, a film forming aid, a water-based defoaming agent, an ultraviolet absorber, and a wetting dispersant.
8. A method of making a UV matte ink according to any of claims 1 to 7, comprising the steps of:
(1) Dropwise adding dibutyltin dilaurate into the polyurethane prepolymer under the stirring state, adjusting the temperature to 50-70 ℃, dropwise adding polyethylene glycol acrylate, stirring for 10-15h, defoaming in vacuum, adding acrylic acid functional monomers, stirring uniformly, adding deionized water, and stirring at the speed of 500-1500r/min for 1-2h to obtain a water-based composite polyurethane emulsion;
(2) And adding UV gloss oil, an active agent, a photoinitiator, a pigment and an additive into the water-based composite polyurethane emulsion, and uniformly mixing to obtain the UV frosted ink.
9. A method of using the UV frosted ink according to any of claims 1 to 7, wherein after printing the UV frosted ink, the UV frosted ink is placed in a UV oven with a wavelength of 365nm for photopolymerization for 1 to 2 hours.
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